THERMAL

COKDUCTIVITY
OF LIQUIDS

3017

Thermal Condilnctivity of Liquids

by Sheng Hsien Lin, Henry Eyring, and Walter J. Davis

Department of Chemistry, University of Utah, Salt Lake City, Utah

(Received J u n e 1 , 1965)

The significant structure theory of liquids is applied to calculate the thermal conductivities of liquids. Pressure and temperature effects on thermal conductivities are discussed. For the three substances, nitrogen, argon, and methane, the discrepancy between
the calculated and experimental results is less than 4y0.

I. Introduction
Application of the method of significant structure
theory to both thermodynamical and transport properties of liquids has been made with good
The purpose of this paper is to examine the thermal
conductivity of liquids based on the significant
structure model, ie.
K1

(V,/V)K,

+ (1 - V5V)Kg

(1)

where K I is the contribution to the liquid thermal

conductivity, K , is the Contribution by the solidlike or lattice vibrational degrees OF freedom, and IClz
is the contribution by the gas-like or fluidized degrees
of freedoin. For the calculation of K,, we use the
phonon theory first developed by Peierls4 6 and then
the con-.
modified by Kleniene6 and C a l l a ~ a y . Since
~
tribution of K , to the liquid thermal conductivity irr
sinall, generally less than 5% except in the critical
region, we use the idleal gas formulas for the calculation of K,. Three substances-argon, nitrogen, andl
methane-are chosen for calculating the liquid therim I
conductivity. Pressure and temperature effects on
the thermal conductivity are also discussed.

11. Thermal Conductivity of Solids

When a temperature gradient is applied to a solid,
the equilibrium state will be disturbed, and the average
distribution of phonons should be determined from
the Boltzmann equation
- C,

grad T d N / d T

blV/bt

(2)

where N is the number of phonons per unit volume and

C, the group velocity of solids. The left-hand side of
eq. 2 represents the rate of change of N due to the
transport of phonons, and this is balanced by the rate

of change due to scattering processes indicated on the

right-hand side. Since the exact solution of eq. 2 is
i~npossible,~
an approximation is made by putting6

N=Nfl+n
(3)
Where N Q is the equilibrium distribution, Nfl =
- l)-. It is apparent that if the temperature gradient is small, then n << NO, so dn/dT <<
dNO/dT thus
C ; i T dNo,fdT = b N / d t

(4)

In t e r m of phonons, the heat current is just the energy

flux due to the transport of phonons each of which
+
carries energy hw, so if we let f(k)dk represent the
number of nornial modes in the wave-number interval
and
dc, we obtain for the heat flux in the direc+
tion of V T

where the suinmation is over different polarizations.

+
Since N,O(Ic) == N,O(-k), N,(lc) in eq. 5 can be re+
placed by n,(Ic),i . e . , only the deviation n3 contributes
to the heat flux, because the integration in eq. 5 over
(1) G. Blomgren, A . m . S . Y . Acad. Sci., 79, 781 (1959).
(2) C. M. Carlson, Theory of Fused Salts and Molten Metals.
Doctoral Dissertation, University of Utah, 1960.

(3) E. J. Fuller, Significant Liquid Structures, Doctoral Dissertation, University of Utah, 1960.
(4) R. Peierls, A n n . Phys., 3, 1055 (1929).
(5) R. Peierls, Quantum Theory of Solids, Oxford Cniversity

Preas, London, 1955.

(6) P.G. Klemens, Proc. R o y . SOC.(London), A208, 108 (1951).
(7) J. Callaway, P h y s . Rei.., 113, 1046 (1959).

Volwme 68, S u m b e r 10 October, 1,904

S. H. LIN, H. EYRIKG,
AND W.J. DAVIS

3018

the equilibrium distribution N t vanishes. This is

generally the case for the transport phenomena in
nonequilibrium statistical mechanics.
Next we assume that the discontinuous processes
tend to obliterate exponentially any deviations from
equilibrium, L e .
dN,'dt

- N")/r =

-(N

-TL/T

(6)

where r is an over-all relaxation time and is assumed

to be dependent on w and T . For an isotropic solid,
we may use spherical coordinates in k-space with the
axis of symmetry in the direction of temperature gradient. If we let e be the angle between 12 and grad T ,
eq. 4 becomes, after substitution of eq. 6 into eq. 4
n

TC, cos 0 dT/dZ X dNo/dT

where I , = rjC,, the relaxation path length. and C,, =

(NC&)/V,, the heat capacity of solids per unit volume
for the j t h polarization. Equation 12 has been used
by Kittelll to explain the thermal conductivity of
glasses at' low temperatures. If no distinction is made
between polarizations, eq. 12 can be written as

where R = N k ,the gas law constant, and C, is the sound

velocity of solids.
As with Klemens,Gwe assume that each scattering
process can be represented by a relaxation time, i e . ,
1 / ~
=
l / r ~and
, existence of the following processes
1

(rC, hw)Cph COS 0 d T i d Z

(7)

where C p h is the specific heat of phonons. Combining

eq. 7 and 5 and integrating the angular parts of eq. 5,
we obtain

4./3

dT/dZ

Sr,(k)C,,(k)'C,h~(k)f(k)dk

(8)

or

K,

4 ~ / 3 Sr,(k)C,,(k)2Cph,(k)f(k)
dk

(8a)l

r-l

Because of lack of knowledge of crystal vibrational

spectra, it is impossible to integrate eq. 8a exactly.
If Debye's model is used, then we have
4nf(k) dk

is assumed: (1) normal three-phonon processes where

the relaxation timeg is taken to be proportional t o
( w * T ) - ~(;2 ) the Uinklapp process with a relaxation
time proportional to (e-"/TozT)-l where a is a constant
characteristic of the vibrational spectrum of the material; (3) lattice imperfection scatteringG"' whose
relaxation time is independent of temperature and proportional to m-*. The other processes such as size
effect, etc., are neglected because we are interested
only in high temperature regions. Thus we can write

4.
v2dv
C,

3-

471.02ddw
c,3(a). 3

= __-

(9)

where v is the frequency. If no distinction is made

between longitudinal and transverse phonon^,^ eq. 8a
becomes

Ao4

+ BTw2

(14)

where A o 4 represents the scattering by lattice imperfections, and the term B T d includes the normal and
Umklapp processes. Combining eq. 14 and 13 we
obtain

111. Thermal Conductivity of Gases

Various formulas for the thermal conducfivity of
gases I<, are derived from kinetic theory.12 The general
results are usually expressed as

where is the over-all relaxation time, and omax

the
Debye cut-off frequency. Equation 10 has been used
to explain the thermal conductivity of solids a t low
temperature s ~ c c e s s f u l l y . ~ - ~ ~
From the specific heat theory of solids, we know
that in the high temperature region the Einstein model
is a good approximation. With this approximation,
we have
4 ~ f ( k dk
)

N ' 1 1 , 6 ( ~-

we)

do

(11)

where w e is the Einstein characteristic frequency, N is

Avogadro's number, and S(o - w,) Dirac's &function.
Substituting eq. 11into eq. 8,l \$-eobtain
The Journal of Physical Chemistry

K,

eqKCve

(16)

where E is a pure number, 7, the viscosity, and C,, the

specific heat a t constant volume. As we already
mentioned, the contribution of gas thermal conductivity
to the liquid thermal conductivity is generally small
For our present purpose, therefore, we may use the
(8) B. A. Agrawal and G. S. Verma, Phgs. Rez., 126, 25 (1962).
(9) J. Callaway and H. C. von Baeyer, ibid., 120, 1149 (1960).
(10) P.,
Carruthers, Rev. M o d . Phys., 33, 92 (1961).
(11) C. Kittel, Phgs. Rec:., 7 5 , 972 (1949).
(12) L. B. Loeh. "Kinetic Theory of Gases." McGraw-Hill Book Co.,
Inc., New York, N. I-.,
1927, Chapter G .

THERMAL
CONDUCTIVITY

OF

LIQUIDS

3019

ideal gas equations for E, vn, and CIp, namely, E = (9y 5j/4, where y is the ratio of specifc heat at constant
pressure to that at constant volume, and vS = mE/
(34271.~79,where m is the mass of a molecule, ~7 the
molecular diameter and the average velocity, E =
( 8 h - T / ~ 1 n ) ~ For
~ . the temperature and pressure
ranges of concern, K g is less than or around 5 X
cal./cm. deg. for all three substances. For the rigorous
treatment of K,, one should refer to the literature. l 3 , l 4

IV. Thermal Conductivity of Liquids

Substituting eq. 15 and 16 into eq. 1, we obtain the
equation for the liquiid thermal conductivity as
K1 =

RC,
(huekT)ZPekT V - V ,
-~
ErlgCVg
V(A + BIT) ( e h w e / h T V

r
I

120

80

I
200

160

O K

Figure 1. Temperature dependence of K1 of argon:

, experimental values; A, calculated values;
curve 1. P = 48 atm., curve 2, P = 120 atm.

(17)
where A = Arne4and B = Brne2. The first term on
the right-hand side cif eq. 17 represents the contribution
to thermal conduction due to the vibration of molecules
sitting near equilibrium position and the second term,
the contribution due to the random motion of molecules. For kw,/kT < 1, we may put x 2 e x / ( e x- 1j2 =
1 ; this is generally the case for the liquid therrnal
conductivity. Furthermore, if the pressure is not very
large, C, is constant, and it is convenient to absorb
C, and R into constaints A and B.
The temperature range considered in this paper is
from the normal melting point to the critical temperature for the three substances. For argon, we use P :=
12 atm., T = 106.1K., K , = 2.44 X
cal./deg.
cm., and P = 12 atni., T = 93.6OK., K1 = 2.81 X
cal./deg.
with C, = 1310 im./sec.l6 to calculate the parameters A and B. They are 2.50 ;<
and 5.52 X
for A and B , respectively,
using we = 7.85 X
The corresponding values
obtained for nitrogen and methane are A = 1.82 ><
lO-*O, B = 5.64 X
and A = 1.60 X
B ==
1.77 X
respectively. Below the critical ternperatures, the liquid thermal conductivity is nearly a
linear function of temperature at constant pressure as
shown in Fig. 1 and 2.
To consider the pressure effects on the liquid thermal
conductivity, we USE C, = ( y , / p , / ? ~ ) ~ to estimate the
dependence of C, on the pressure, where y, is the ratio
of specific heats of solids, p,, the density of solids, and
PT, the isothermal compressibility coefficient of solids.
C, does not vary very much with pressure, so we have
to consider the pressure dependence of C, only a t very
high pressures. Because of being limited by the availability of data for @I, only two values of Kl under the
pressure of 8 0 0 K , / c n ~have
~
been calculated for argon.
The data used for the calculation are P = 0, PT = 6.2

4,00r

80

120
T

I60
OK

Figure 2. Temperature dependence of Kl of nitrogen:

, experimental values; A, calculated values;
curve 1, P = 33.5 a t m . ; curve 2, P = 134 atm.

X
~ n i . ~ / K and
, , P = 8 0 0 K , / ~ m . ~PT, = 4.36 x
10-j c n ~ . ~ / K , .V~ ~= 28.89 ~ i n . ~ / m o laet T = 119.6
OK.; V = 27.54 ~ r n . ~ / m o l at
e l ~T = 102.2 OK. The
results obtained by using eq. 17 are K 1 = 3.30 X
cal./deg. cni. at P = 8 0 0 K , / ~ n i . ~T, = 119.6OI<.,
cal./deg. cm. at P = 800K,/
and K1 = 3.91 X
cni.2, T = 10%.2OK.,in comparison with the extrapolated experiiiiental values of Rice.Ig K 1 = 3.40 X
(13) J. 0. Hirschfelder, C. F. Curtiss, and R. B. Bird, Molecular
Theory of Gases and Liquids, John Wilzy and Sons, Inc., New
York, N. Y . , 1954.
(14) S.Chapman and T. G. Cowling, The Mathematical Theory of
Non-uniform Gases, Cambridge University Press, London, 1953.
(15) H. Ziebland and J . Burton, Brit. J . A p p l . Phys., 9, 52 (1958).
(16) J. W. Stewart, J . Phys. Chem. Solids, 1, 146 (1956).
117) E. J. Fuller, T. Ree, and H. Eyring, Proc. S a t l . Acad Sci.
U . 8 , 45, 1594 (1959).
(18) P. W. Bridgman, Proc. Am. Acad. A r k Sci., 70, 1 (1935).
(19) L. D. Ikenberry and S. A. Rice, J . Chem. Phys., 39, 1961
(1963).

Volume 68, Yumber 10

October, 156.4

3020

S.H. LIN, H. EYRISG,AXD W. J. DAVIS

Table I : Results of Calculation"

1 -,

3.00
rs

Pressure,
atm.

93.3
93.3
93.3
130
120
125.7
125.7
140
150.7d
102,2
119.6

48
72
120
48
48
48
19.3
72
48
48d
774
774

'

2.00

I .

87.7
87.7
87.7
98.3
105.8
105,8
105.8
116.1
126, Id
80

Nitrogenb
134
3.18
67
2.93
33.5
2.88
67.0
2.53
33.5
2.20
50.3
2.24
100.5
2,50
33.5
1.83
33, 5d
1.04
33.5
3.22

Figure 3. Pressure effert on K1 of argon:

experimental results; A, calculated values;
curve 1, T = 93.3"K.; curve 2, T = 106.lOK.
~

3.00

A 'A

.-

P atm
Figure 4. Pressure effect on Ki of nitrogen:
---, experimental results; A, calculated values;
curve 1, T = 87.7"K.; curve 2, T = 105.6"K.

cal./deg. cm., K1 = 3.80 X

cal./deg. cm.,
respectively. The liquid thermal conductivity us.
pressure for pressures below 140 atin. are shown in
Fig. 3 and 4. It can be seen that for small ranges of
pressure, K I is linear with respect to pressure.
Sonie of the calculated results of Kl for the three
substances are tabulated in Table I, in comparison with
the experimental values. The discrepancy, as can be
seen from the table, is less than 4y0. In concluding
this paper, it is interesting to notice that Ks's calculated
from eq. 15 by using the values of A and B obtained
from liquids are in good agreement with the experimental values of K,; for example, a t P = 180 atm.,
T = 83.6'K., K , (calcd.) = 4.29 X
cal./deg. cm.,
K , (exptl.) = 4.27 x
cal./deg. cni.,15and a t T =
77OK., K , (calcd.) = 4.22 X
cal./deg. cm., K ,
(exptl.) = 4.20 x 1 0 - ~cal./deg. cm. If this is the
case, we may assert that the structure of the solid part
of liquids is not much different from that of solids at
high temperatures, but in view of the limited amount

The Journal of Physical Chemistry

K I (calod.) X 104, Ki (exptl.) X 104,

cal./deg. cm.
cal./deg. om.

Argon'

_-_

Temp.,
OK.

100

99.0
99.0
125.6
150.3
150.3

1.6
50.5
50.1
25.9
49.7

2.87
2.89
2.96
2.68
1.84
2.1c
1.89
2.01
1.54
0.914
3.91
3.30

Methane"
4.97
5.01
4.05
3.26
3.30

2.90
2.93
3.04
2,70
1 .793
2.11
1.88
1.99
1.48
3.80"
3 , 4OC
3.14
2.97
2.90
2.60
2.17
2.25
2,46
1,75
3.26
4,946
5.06
4.096
3.176
3.284

a V , = 22.5 ml./mole for argon, 26.14 ml./mole for nitrogen,

Experiment'al data of Ki
and 30.90 ml./mole for methane.
are from H. Ziebland and J. Burton, Brit. J . A p p l . Phys., 9, 52,
(1958).
Experimental data of K I are from L. D. Ikenberry
and S. A. Rice, J . Chem. Phys., 39, 1961 (1963).
The wittical
point. The data used to calculate A and B are P = 8.4 atm.,
T = 88.2"K., K I = 2.79 X 1 0 - 4 , a n d P = 27.6atm., T = 80.9"K.,
K l = 3.18 X lo-* for nitrogen, and P = 25.3 atm., T = 99"K.,
K I = 4.999 X
and P = 24 atrn., T = 125.6"K.,Ki = 4.016
X
for methane.

'

of data of K , at high temperatures (2' > eo, Debye's

characteristic temperature) which are available, it
seems that further justification is necessary.
Acknowledgment. Acknowledgment is made to the
Army Ordnance under Contract DA-ilRO(D)-31124-G298 for financial support of this research.